CN103572071B - A kind of method of refining lithium from salt lake brine with high magnesium-lithium ratio - Google Patents
A kind of method of refining lithium from salt lake brine with high magnesium-lithium ratio Download PDFInfo
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Abstract
The invention discloses a kind of method of refining lithium from salt lake brine with high magnesium-lithium ratio, comprising: 1) carry the bittern after sodium, potassium through removing sulfate radical, obtaining boron-rich lithium bittern through evaporation; 2) boron-rich lithium bittern obtains boric acid and rich lithium acidizing fluid through acidifying; 3) use the rich lithium acidizing fluid of nanofiltration membrane separation, obtain once dense water and once produce water; 4) the once product water warp that step 3) obtains takes off boron, obtains producing water without the rich lithium of boron; 5) produce water without the rich lithium of boron and obtain secondary product water and fresh water through reverse osmosis; 6) secondary product water evaporates after demagging, obtains the rich lithium bittern after refining.Salt field process and membranous system are closely linked by the present invention, make full use of sun power, pressure equal energy source power, greatly reduce energy consumption, and technical process is simple, improve the rate of recovery of lithium ion, reduce production cost and safety coefficient, fundamentally solve being separated and enrichment of sulfate type and lithium ion in the high Mg/Li ratio bittern such as chloride type.
Description
Technical field
The invention belongs to Salt Lake Chemistry field, be specifically related to a kind of method of refining lithium from salt lake brine with high magnesium-lithium ratio.Background technology
Lithium is metal the lightest in the world, and due to its special property, lithium and compound thereof have extensive and special purposes, is described as " energy metal " and " promoting the metal that the world advances ".In industries such as energy industry, aerospace industry, Metal smelting and process industry, refrigeration, pottery, glass, play extremely important effect.The current whole world is very urgent to the demand of lithium product, the demand rapid growth year by year of lithium.
The first resource of lithium is lithium ore in the world, mainly contains the mineral such as triphane, lithionite, petalite, amblygonite and eucryptite.The mining industry of tradition lithium mainly extracts lithium product by strong energy and chemical recovery technique in pegmatite type lithium ore deposit, needs by mining, ore dressing, 1100 DEG C of roasting pyrolysis, and 250 DEG C add sulfuric acid and form vitriol, then adds alkali filtration formation Quilonum Retard.Obtain the product of metallic lithium in this way, because processing process is long, energy consumption is large, its production cost is higher.
Second Main Resources of lithium is containing the high salt lake brine of lithium.It is carry out stepped evaporation by a series of sun evaporation tank to bittern to concentrate that salt lake brine puies forward lithium technique, isolates lithium salts or High Concentration Brine, is then purified by factory and produces lithium salts; The energy of the course of processing is based on sun power, and technique is simple, and industrial scale is easy to adjustment, and therefore cost reduces greatly.Current world lithium salts ultimate production more than 80% from salt lake brine.
In salt lake brine containing various ingredients as the isoionic muriate of sodium, potassium, magnesium, calcium, boron, lithium, vitriol and carbonate etc.Its component difference of different salt lakes is very large, thus determines the complete processing difference that saline lake lithium resource development & construction adopt.Generally speaking, in salt lake brine, the height of Mg/Li ratio value determines and utilizes Brine resources to produce the feasibility of lithium salts and the production cost of lithium salts product and economic benefit.The external salt lake brine that why can utilize produces lithium compound, is because the Mg/Li ratio value of its bittern is little.As the silver-colored peak subsurface brine of the U.S., Mg/Li ratio is only 1.5:1; The Atacama salt lake of Chile, Mg/Li ratio is 6.25:1, can adopt salt pan concentration technique, by the lithium enrichment in bittern, then rich lithium bittern is sent into factory, produces lithium product.
The salt lake resources of China is enriched, of a great variety, is mainly distributed in four provinces and regions such as Qinghai, Xinjiang, Tibet and the Inner Mongol.Lithium resource reserves are large, and the salt lake, the Caidamu Basin that the salt lake brine that content is high focuses mostly in Qinghai Province, as: the platform Ji salt lake such as lake, Yi Liping, Cha Er Han and large Chai Dan like this, has very high extraction value and huge potential economic benefit.But because Mg/Li ratio numerical value is comparatively large in its performance history, directly bring the difficulty in exploitation.
The salt lake brine type that China's Qinghai lithium resource enriches mostly is sulfate type and chloride type bittern, and containing a large amount of magnesium in bittern, Mg/Li ratio value is high, minimum about 40, reaches as high as hundreds of even thousands of.High Mg/Li ratio significantly limit separation and the enrichment of lithium in bittern, and this also becomes the key factor of restriction China saline lake lithium resource development and application.The lithium of current China more than 80% needs import, effectively the domestic saline lake lithium resource of development and utilization, can improve China's lithium industry competitive power in the world.And solve the difficult problem that in bittern, magnesium lithium is separated, realize separation and the enrichment of lithium ion in bittern, obtain highly purified Quilonum Retard and other lithium salts product, become the key of China's saline lake lithium resource exploitation and large-scale production.
At present, salt lake brine puies forward the method for lithium, generally comprises following following several:
(1) evaporative crystallization partition method:
The method comprises a series of evaporative crystallization in conjunction with other extraction process, first from bittern, reclaims the useful components such as sodium, potassium, boron, bromine, iodine, then carry lithium from last mother liquor.The key putting forward lithium technique removes calcium, the magnesium in mother liquor.The method generally uses caustic soda demagging, adds soda ash precipitated calcium, and last concentrated mother liquor soda ash precipitates Quilonum Retard.
Although the method can reclaim the different kinds of ions such as sodium, potassium component from bittern, put into practice verified: simple evaporative crystallization other all ion not divisible; And along with the carrying out of evaporating, concentration, the mobility of bittern all have a great impact solid-liquid separation, and in bittern, the loss of lithium ion can improve greatly.
(2) precipitator method
The precipitator method are in the bittern higher containing lithium, add certain precipitation agent and are precipitated out from material solution by lithium, and then select certain reagent to be leached by lithium.The current precipitator method comprise carbonate precipitation method, the aluminate precipitator method, hydrated sulfuric acid lithium crystalline deposit method and boron magnesium, boron lithium coprecipitation method etc. from extracting lithium from salt lake brine.The method is easy to industrialization, but requires harsh to bittern, is only applicable to the bittern that Mg/Li ratio value is low
(3) organic solvent extractionprocess
Organic solvent extractionprocess utilizes different organic solvents as extraction agent, extracted by lithium from bittern.The method is from low grade brine, put forward the effective method of lithium, and the conventional system extracting lithium from bittern mainly contains single extraction system and synergistic system two class.Although organic solvent extractionprocess has, raw materials consumption is few, efficiency advantages of higher, and this method exists the molten damage of extraction agent and the problem such as equipment corrosion is large, still rests on the discussion of theoretical side at present, does not form the productivity of reality.
(4) ion exchange adsorption
Ion exchange adsorption utilizes to the sorbent material of the selective absorption of lithium ion to adsorb lithium ion, then eluted by lithium ion, reaches the object that lithium ion is separated with other foreign ion.Ion exchange adsorption is mainly applicable to carry lithium from containing the lower bittern of lithium.Ion adsorbent can be divided into mineral ion sorbent material and organic ion sorbent material.Ion adsorbent has higher selectivity to lithium, but these attached dose of price is high, and adsorptive capacity is low, very easily contaminated, and in addition, the requirement of strength of this method to sorbent materials such as resins is high.
(5) leaching method is calcined
Calcining leaching method comprises anhydrates 50% by bittern evaporation after carrying boron, and obtain four aqueous magnesium chlorides, at 700 DEG C of calcining 2h, obtain magnesium chloride, then add water extraction lithium, lithium leaching rate more than 90%, leaching liquid is containing lithium about 0.14%.Again with milk of lime and the soda ash removing impurity such as calcium, magnesium, being concentrated into by solution containing lithium is about 2%, after add soda ash and be settled out Quilonum Retard, the yield about 90% of lithium.Magnesium chloride slag after calcining, can obtain through refining the magnesium chloride byproduct that purity is 98.5%.Calcining leaching method has fully utilized the resources such as magnesium lithium, and raw material consumption is few, but magnesium utilization makes flow process complicated, and equipment corrosion is serious, and need the water yield of evaporation comparatively large, power consumption is large simultaneously.
(6) electroosmose process
Electroosmose process comprises and concentrates old halogen by one or more levels electrodialyzer by containing magnesium lithium salts lake bittern water or salt pan Exposure to Sunlight, monovalent cation selective ion exchange membrane and univalent anion selective ion exchange membrane (continous way, sequential portion circulating or batch circulation formula) technique of carrying out circulating is utilized to concentrate lithium, obtain the low magnesium bittern of rich lithium, then deep impurity-removing, refining concentrated, just can produce Quilonum Retard or lithium chloride.Electroosmose process effectively can realize magnesium lithium and be separated, but in operational process, can produce a large amount of hydrogen and chlorine, is unfavorable for the enforcement of technique; The electric energy of palpus at substantial, carries lithium cost and greatly improves simultaneously.
(7) Xu Shi method
Method inhaled by " Xu Shi method " i.e. pump, is a kind of novel method carrying lithium from bittern that Polytechnics of Swiss Confederation Institute of Geology professor Xu Jinghua proposes based on " evaporation pump principle " and " original place chemical reaction pond method ".This method is only applicable to arid, the semiarid zone that steam output is far longer than quantity of precipitation.Xu Shi method cost is low, actual effect is high, productive rate is high, and actual field trial shows, although the concentration of lithium ion in bittern can be made to raise, but still have a large amount of magnesium in bittern, Mg/Li ratio value is still very high, far away for reaching the bittern index producing Quilonum Retard.
(8) nano filtering process
Nanofiltration membrane separation inorganic salt technology is a kind of novel membrane separation technique.Nanofiltration membrane is a kind of pressure drive membrane, due to normal with charged group on film or in film, by electrostatic interaction, produce Donnan effect, to the ion of different valence state, has different selectivity, thus realize the separation of different valence state ion.In general, the rejection of nanofiltration membrane to monovalent salt is only 10% ~ 80%, have sizable perviousness, and the rejection of divalence and a polyvalent salt is all more than 90%, achieves being separated of lithium ion and magnesium ion.Nanofiltration membrane has the common energy-efficient feature of membrane technique, and at present at domestic water, the process of industrial water and waste water, food, the fields such as biochemical pharmacy are widely used.
Application number be 03108088.X, 201010295933.X with 201310035015.7 Chinese patent application disclosed and use nanofiltration membrane to realize magnesium lithium to be separated, but application number bittern condition disclosed in the patent application of 03108088.X is too wide in range, do not consider the suitability of equipment, practical significance is little; Application number is that the patent application of 201010295933.X has carried out part improvement to it, but the dense water that recycle nanofiltration obtains in nanofiltration membrane system, the Mg/Li ratio value that nanofiltration can be caused to produce water raises greatly, adds the progression of nanofiltration membrane system; In addition, this application does not consider other ion in actual polycomponent bittern in the process of nanofiltration membrane separation to the impact that magnesium lithium is separated, and does not consider the impact of film properties on magnesium lithium separating effect, has certain limitation in actual applications; Application number be 201310035015.7 Chinese patent application disclosed nanofiltration membrane and carried out the separation of magnesium lithium, and carried out actual bittern test, magnesium lithium separation aspect is respond well, but inevitably there is shunting in boron in by the process of nanofiltration membrane, the transmitance of boron reaches 20%, if do not removed, produce impact greatly by the quality of the Quilonum Retard finally obtained or other lithium salts product, greatly reduce the quality of product.
Summary of the invention
The object of the present invention is to provide a kind of method of refining lithium from salt lake brine with high magnesium-lithium ratio; utilize salt field process and membranous system equipment; make full use of the advantage of sun power and pressure membrane; simply, efficiently, solve the difficult problem that bittern magnesium lithium is separated greenly, energy-conservation; and reduce the impact of impurity element on Quilonum Retard or other lithium salts product; obtain high purity lithium product salt; fundamentally solve being separated and enrichment of vitriolate type bittern and lithium ion in chloride type bittern, realize production demonstration and large-scale production.
The method of refining lithium from salt lake brine with high magnesium-lithium ratio provided by the invention, comprises the steps:
1) carry the bittern after sodium, potassium and obtain boron-rich lithium bittern through removal sulfate radical, evaporation.
The relatively low Mg/Li ratio of above-mentioned high Mg/Li ratio, the Mg/Li ratio 1.28 in such as Bange lake-Du Jiali salt lake, it is generally acknowledged high Mg/Li ratio be Mg/Li ratio higher than 20, such as 20 ~ 3000.
Preferably, the Mg/Li ratio carrying the bittern after sodium, potassium described in is 30 ~ 150:1.
Find in old halogen evaporation test process, sulfate radical reduces bittern Mg/Li ratio value to salt pan evaporation great retardation effect, therefore must remove sulfate radical, prevent it to the interference of follow-up treating process.The removal of sulfate radical is that the mode that sulfate radical is separated out as gypsum realizes, the bittern after the sulfate radical that is simultaneously removed by adding calcium chloride or its saturated solution in the bittern after carrying sodium, potassium.The further salt pan evaporation of bittern after removing sulfate radical, can separate out a large amount of bischofites, reduce the Mg/Li ratio value of bittern, improve the concentration of boron and lithium in bittern simultaneously.Preferably, in described boron-rich lithium bittern, the concentration of boron is greater than 10g/L, and Mg/Li ratio value is not higher than 20.
2) boron-rich lithium bittern obtains boric acid and rich lithium acidizing fluid through acidifying.
Owing to realize the separation of magnesium lithium at nano filtering process while, inevitably there is shunting in the boron in bittern, the transmitance of boron reaches 20%, if do not remove boron impurity, produce impact greatly by the quality of the Quilonum Retard finally obtained or other lithium salts product, greatly reduce the competitive power of product.Therefore, first must remove the boron in bittern, then enter follow-up nanofiltration membrane system and carry out the separation of magnesium lithium.
The method of boron from brines is a lot, and the production cost carrying boron with acidization is minimum.Bittern is acidified obtains boric acid, and the transformation efficiency of this stage boron is 60 ~ 70%, still has the boron of 30 ~ 40% to be present in acidified filtrate.And carry in boron process in acidifying, lithium is almost without any loss.
Preferably, described acidifying functional quality concentration be 18 ~ 30% hydrochloric acid carry out.
3) use the rich lithium acidizing fluid of nanofiltration membrane separation, obtain once dense water and once produce water, produce water Mg/Li ratio value and be reduced to less than 2.
A kind of film separating system comprising nanofiltration membrane is additionally provided in embodiments of the invention, comprise nano filter membrance device and reverse osmosis membrane apparatus, assembled by raw water box, submersible pump, cartridge filter, purpose ceramic-film filter, high-pressure pump, membrane module, inlet chest, product water tank, dense water tank and frame etc.Rich lithium acidizing fluid fresh water is diluted, is stored in raw water box, utilizes submersible pump, bittern after dilution is pumped in membranous system, through cartridge filter and ceramic membrane device, pre-treatment is carried out to bittern, is transferred in inlet chest.Open high-pressure pump, under pressure-driven, in inlet chest, bittern is pumped in nano filter membrance device, and in membrane element, water inlet is divided into product water and dense water two portions.Wherein once product water is the bittern through film, and lithium content is high, and Mg content is extremely low, and Mg/Li ratio value is very low; And once dense water is the bittern that tunicle retains, Mg content is high, and lithium concentration is lower, and Mg/Li ratio value improves greatly.Thus reach the object of magnesium lithium separation.
Preferably, described step 3) also comprises pre-dilution step, dilutes by rich lithium acidizing fluid, and the rich lithium acidizing fluid after dilution is separated by nanofiltration membrane again.Preferably, this step is by rich lithium acidizing fluid dilution 10 ~ 20 times.Preferred, this step is by rich lithium acidizing fluid dilution 12 ~ 18 times, and rich lithium souring soln is diluted 15 times in one embodiment of the invention, and achieves good effect.
Preferably, described step also comprise by part once dense water return, and with enter rich lithium acidizing fluid mix after again by carrying out nanofiltration membrane separation.Now, membranous system adopts dense water internal-circulation type membranous system (membranous system loading reverse flow valve), in nanofiltration separation process, part once dense water directly get back to the import of nanofiltration membrane, and with rich lithium acidifying liquid-phase mixing.Dense water cycle can make water inlet flow rate kept constant in membrane module, and between film import to outlet, pressure is consistent, and system salt permeability is higher, substantially increases the efficiency of nanofiltration separation and the system recoveries rate of lithium, decreases the progression of nanofiltration.Test shows, by one-level nanofiltration, just product water Mg/Li ratio value can be down to less than 2.
4) the once product water that step 3) obtains takes off boron through the degree of depth, obtains producing water without the rich lithium of boron.
In this step, because shunting inevitably appears in boron in nanofiltration membrane system, is produced from water side in nanofiltration, and the transmitance of boron reaches 20%; But carry boron stage most boron due to acidifying and form boric acid, and before entering nanofiltration membrane system, bittern is through dilution, the nanofiltration finally obtained is produced in water, and the concentration of boron is extremely low (about 20 ~ 60ppm).
Preferably, this stage adopts boron resin adsorption deeply except boron, compared with boron extraction, will greatly reduce except boron cost, and the rich lithium finally obtained produces in water without boron.
5) utilize reverse osmosis unit concentrated without boron rich lithium product water, obtain the secondary after concentrating and produce water and fresh water.
Utilize reverse osmosis membrane apparatus, the concentration of lithium ion in water is produced in enrichment nanofiltration.Under pressure-driven, produce water without the rich lithium of boron and be pumped in reverse osmosis membrane apparatus, in membrane element, water inlet is divided into dense water and fresh water two portions.Wherein dense water is enrichment bittern, and in bittern, lithium ion is concentrated, and concentration improves greatly; Hardly containing any salt component in fresh water, suitable with deionized water.Fresh water can be back in nanofiltration membrane system, as the diluting water of rich lithium acidizing fluid, decreases the add-on of fresh water, has saved water resources.
Preferably, step 5) also comprises produces water section by secondary and returns, and carries out reverse osmosis isolation with producing after water mixes without the rich lithium of boron.Reverse osmosis membrane system adopts dense water internal-circulation type membranous system equally, improves the efficiency of reverse osmosis concentration, decreases the progression of reverse osmosis.
6) secondary product water evaporates after demagging, obtains the rich lithium bittern after refining.
In order to reach the bittern lithium concentration requirement needed for prepared calcium carbonate lithium, water must be produced by concentrated secondary further.First through degree of depth demagging, the magnesium ion remained in bittern is eliminated.Recycling sun power carries out salt pan evaporation, makes lithium concentration in rich lithium bittern reach 33 ~ 38g/L.Then rich lithium bittern is transferred to Quilonum Retard production plant, high purity lithium carbonate product.What obtain recycles containing lithium mother liquor, improves the recovery utilization rate of lithium.
Preferably, described method also comprises: step 7):
Once dense water step 3) obtained, through reverse osmosis membrane separation, obtains fresh water and the dense water of secondary, the dense water of described secondary be used for and sulfate radical after bittern mixing convert halogen, then carry out salt pan evaporation separate out bischofite.
Nanofiltration membrane system is carried out in the process of magnesium lithium separation, and still some is retained in dense water side to lithium, and rejection reaches 30 ~ 35%, recycles, will greatly improve the recovery utilization rate of lithium to it.
The concrete steps recycling lithium are: first utilize reverse osmosis membrane apparatus, the concentration of the dense water of enrichment nanofiltration.Under pressure-driven, the dense water of nanofiltration is pumped in reverse osmosis membrane apparatus, and in membrane element, water inlet is divided into dense water and fresh water two portions.Wherein dense water side is enrichment bittern, and concentration improves greatly; Hardly containing any salt component in fresh water, suitable with deionized water.Fresh water is back in nanofiltration membrane system, as the diluting water of rich lithium acidizing fluid, can reduce the add-on of fresh water, saving water resource.
Preferably, this step also comprises and being returned by dense for part secondary water, again through reverse osmosis membrane separation after mixing with the once dense water that step 3) obtains.Reverse osmosis membrane system adopts dense water internal-circulation type membranous system, can improve the efficiency of reverse osmosis concentration, decrease the progression of reverse osmosis.
Technique of the present invention has carried out magnifying test, utilizes actual vitriolate type bittern to demonstrate the feasibility of technique.Obtain optimum process condition.
The present invention has following advantage:
(1) technique of the present invention may be used for the process of a large amount of bittern, and through extension verification experimental verification, this technique has very strong feasibility.
(2) compared with putting forward lithium method with existing salt lake, salt field process and membranous system are closely linked by the present invention, make full use of sun power, pressure equal energy source power, greatly reduce energy consumption.
(3) technical process of the present invention is simple, and equipment is easy to configuration, cleaning, installs and transfer, very easily applies, carries out production demonstration and large-scale production.
(4) the present invention refines salt lake brine resource in lithium process and is fully used, and the rate of recovery of lithium ion is greatly enhanced.
(5) present invention, avoiding the impact of boron on Quilonum Retard or other lithium salts product, substantially increase quality and the competitive power of product.
(6) present invention eliminates boron extraction, and follow-up phase adopts the resin degree of depth to carry boron, technique is simplified greatly, and reduces production cost and safety coefficient.
(7) the present invention fundamentally solves the problem of being separated of sulfate type and lithium ion in the high Mg/Li ratio bittern such as chloride type and enrichment difficulty.
Accompanying drawing explanation
Fig. 1, from salt lake brine with high magnesium-lithium ratio the process flow sheet of refining lithium.
Embodiment
Be below a preferred embodiment of the present invention, it is only used as the explanation of the application instead of restriction.
The composition of the old bittern that the present invention selects and the bittern in each stage composition are in table 1, and it is the water of reverse osmosis membrane through side that the present invention arranges fresh water.
1) sulfate radical of the bittern (i.e. old bittern or old halogen) after sodium, potassium are carried in removing obtains boron-rich lithium bittern through evaporation;
In this stage, in the bittern after carrying sodium, potassium, add calcium chloride or its saturated solution, sulfate radical is separated out as gypsum.Proceed the evaporation of bittern salt pan, separate out a large amount of bischofites simultaneously, reduce the Mg/Li ratio value of bittern.In the boron-rich lithium bittern of this step, the concentration of boron is greater than 10g/L, and Mg/Li ratio value is not higher than 20.
Table 1, from salt lake brine with high magnesium-lithium ratio refining lithium each stage bittern composition (g/L)
| Stage | Mg 2+ | Cl - | SO 4 2- | Li + | B 2O 3 | Mg/Li |
| Remove bittern after sodium, potassium | 116.10 | 320.05 | 32.54 | 1.46 | 5.03 | 79.52 |
| Boron-rich lithium bittern | 103.00 | 330.05 | 11.55 | 10.44 | 34.86 | 9.86 |
| Rich lithium acidizing fluid | 99.59 | 326.78 | 10.03 | 10.13 | 8.70 | 9.83 |
| Once produce water | 1.10 | 9.20 | — | 1.17 | 0.12 | 0.94 |
| Water is produced without the rich lithium of boron | 1.10 | 9.20 | — | 1.16 | — | 0.95 |
| Secondary produces water | 4.84 | 39.52 | — | 5.00 | — | 0.97 |
| Rich lithium bittern after refining | — | 176.20 | — | 34.50 | — | — |
| Once dense water | 13.26 | 40.90 | 1.11 | 0.60 | 0.79 | 22.10 |
2) boron-rich lithium bittern obtains boric acid and rich lithium acidizing fluid through acidifying.
Boron-rich lithium bittern is acidified obtains boric acid, and the transformation efficiency of this stage boron is 60 ~ 70%, still has the boron of 30 ~ 40% to be present in acidified filtrate.And carry in boron process in acidifying, lithium is almost without any loss.In this step acidifying functional quality concentration be 18 ~ 30% hydrochloric acid carry out.
3) use the rich lithium acidizing fluid of nanofiltration membrane separation, obtain once dense water and once produce water, produce water Mg/Li ratio value and be reduced to less than 2.Described nanofiltration membrane is the film to divalence and polyvalent ion preferential rejection, and those skilled in the art can select the corresponding film of DK, DL and the Dow Chemical Company as GE company as required, and in the present embodiment, nanofiltration membrane selects DK film.
Being separated rich lithium acidizing fluid uses membranous system to carry out, this system comprises nano filter membrance device and reverse osmosis membrane apparatus, is assembled by raw water box, submersible pump, cartridge filter, purpose ceramic-film filter, high-pressure pump, membrane module, inlet chest, product water tank, dense water tank and frame etc.Rich lithium acidizing fluid fresh water is diluted, is stored in raw water box, utilizes submersible pump, the bittern after dilution 15 times is pumped in membranous system, through cartridge filter and ceramic membrane device, pre-treatment is carried out to bittern, is transferred in inlet chest.Open high-pressure pump, under pressure-driven, in inlet chest, bittern is pumped in nano filter membrance device, and in membrane element, water inlet is divided into product water and dense water two portions.Wherein once product water is the bittern through film, and lithium content is high, and Mg content is extremely low, and Mg/Li ratio value is very low; And once dense water is the bittern that tunicle retains, Mg content is high, and lithium concentration is lower, and Mg/Li ratio value improves greatly.Thus reach the object of magnesium lithium separation.
This step also comprise by part once dense water return, and carry out membrane sepn after mixing with the rich lithium acidizing fluid entering membranous system.Now, membranous system adopts dense water internal-circulation type membranous system (membranous system loading reverse flow valve), and in nanofiltration separation process, the dense water of part directly gets back to the import of nanofiltration membrane, and mixes mutually with water inlet.Dense water cycle can make water inlet flow rate kept constant in membrane module, and between film import to outlet, pressure is consistent, and system salt permeability is higher, substantially increases the efficiency of nanofiltration separation and the system recoveries rate of lithium, decreases the progression of nanofiltration.Test shows, by one-level nanofiltration, just product water Mg/Li ratio value can be down to less than 2.
4) the once product water that step 3) obtains takes off boron through the degree of depth, obtains producing water without the rich lithium of boron.
Because shunting inevitably appears in boron in nanofiltration membrane system, is produced from water side in nanofiltration, and the transmitance of boron reaches 20%.But carry boron stage most boron due to acidifying and form boric acid, and bittern passes through dilution before entering nanofiltration membrane system, the nanofiltration finally obtained is produced in water, the concentration of boron is extremely low (about 20 ~ 60ppm), this stage adopts boron resin adsorption deeply except boron, compared with boron extraction, will greatly reduce except boron cost, and without boron in the rich lithium bittern finally obtained.
5) utilize reverse osmosis unit concentrated without boron rich lithium product water, obtain secondary and produce water.
Utilize reverse osmosis membrane apparatus, the concentration of lithium ion in water is produced in enrichment nanofiltration.Under pressure-driven, nanofiltration is produced water and is pumped in reverse osmosis membrane apparatus, and in membrane element, water inlet is divided into dense water and fresh water two portions.Wherein dense water is that secondary produces water, and in bittern, lithium ion is concentrated, and concentration improves greatly; Hardly containing any salt component in fresh water, suitable with deionized water.Fresh water is back in nanofiltration membrane system, as the diluting water of rich lithium acidizing fluid, decreases the add-on of fresh water, has saved water resources.Reverse osmosis membrane system adopts dense water internal-circulation type membranous system equally, improves the efficiency of reverse osmosis concentration, decreases the progression of reverse osmosis.
6) evaporating after demagging without boron rich lithium product water after concentrating, obtains the rich lithium bittern after refining.
Salt field process concentrates secondary and produces water, improves the concentration of lithium ion in rich lithium bittern further, reaches production requirement.In rich lithium bittern after refining, the concentration of lithium ion is 33 ~ 38g/L, in order to reach the bittern lithium concentration requirement needed for prepared calcium carbonate lithium, must produce water by concentrated secondary further.First through degree of depth demagging, the magnesium ion remained in bittern is eliminated.Recycling sun power carries out salt pan evaporation, makes lithium concentration in rich lithium bittern reach 33 ~ 38g/L.Then rich lithium bittern is transferred to Quilonum Retard production plant, high purity lithium carbonate product.What obtain recycles containing lithium mother liquor, improves the recovery utilization rate of lithium.
7) the once dense water that obtains of step 3) is through reverse osmosis membrane separation, obtains fresh water and the dense water of secondary.
Utilize reverse osmosis membrane apparatus, the concentration of enrichment once dense water.Under pressure-driven, the dense water of nanofiltration is pumped in reverse osmosis membrane apparatus, and in membrane element, water inlet is divided into dense water and fresh water two portions.Wherein dense water side is the dense water of secondary, and concentration improves greatly, for sulfate radical after bittern mixing convert halogen, then evaporation separate out bischofite; Hardly containing any salt component in fresh water, suitable with deionized water, it as the diluting water of rich lithium acidizing fluid, can decrease the add-on of fresh water, has saved water resources.Reverse osmosis membrane system adopts dense water internal-circulation type membranous system equally, improves the efficiency of reverse osmosis concentration, decreases the progression of reverse osmosis.
Claims (7)
1. from salt lake brine with high magnesium-lithium ratio, refine a method for lithium, comprising:
1) bittern after sodium, potassium is carried through removing sulfate radical, obtaining boron-rich lithium bittern through evaporation;
2) boron-rich lithium bittern obtains boric acid and rich lithium acidizing fluid through acidifying;
3) use the rich lithium acidizing fluid of nanofiltration membrane separation, obtain once dense water and once produce water;
4) step 3) the once product water that obtains through de-boron, obtain without boron rich lithium product water;
5) produce water without the rich lithium of boron and obtain secondary product water and fresh water through reverse osmosis;
6) secondary product water evaporates after demagging, obtains the rich lithium bittern after refining;
Step 1) described in boron-rich lithium bittern the concentration of boron be greater than 10g/L, Mg/Li ratio value is not higher than 20;
Rapid 2) in functional quality concentration be 18 ~ 30% hydrochloric acid carry out acidifying;
Step 3) in be separated by nanofiltration membrane again after rich lithium acidizing fluid dilution 10 ~ 20 times;
Step 4) use resin to carry out de-boron.
2. method according to claim 1, is characterized in that, step 3) described in once produce water Mg/Li ratio value not higher than 2.
3. method according to claim 1, is characterized in that, described method also comprises step 3) part that obtains once dense water return, and pass through nanofiltration membrane separation again after mixing with rich lithium acidizing fluid.
4. method according to claim 1, is characterized in that, step 5) also comprise and secondary is produced water section return, carry out reverse osmosis isolation with producing after water mixes without the rich lithium of boron.
5. method according to claim 1, is characterized in that, described refining after rich lithium bittern in the concentration of lithium ion be 33 ~ 38g/L.
6. method according to claim 1, is characterized in that, described method also comprises step 7):
Step 3) the once dense water that obtains is through reverse osmosis membrane separation, and obtain fresh water and the dense water of secondary, the dense water of described secondary is used for and halogen is converted in bittern mixing after sulfate radical.
7. method according to claim 6, is characterized in that, described step 7) also comprise:
Dense for part secondary water is returned, with step 3) the once dense water that obtains mix after again through reverse osmosis membrane separation.
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| CN104372181A (en) * | 2014-11-26 | 2015-02-25 | 中国科学院青海盐湖研究所 | Method for extracting lithium from salt lake brine |
| CN104961143B (en) * | 2015-07-03 | 2017-08-01 | 青海恒信融锂业科技有限公司 | The method that lithium is extracted from salt lake bittern |
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